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The Gibbs–Helmholtz equation is a thermodynamic equation used to calculate changes in the Gibbs free energy of a system as a function of temperature.It was originally presented in an 1882 paper entitled "Die Thermodynamik chemischer Vorgänge" by Hermann von Helmholtz.
In thermodynamics, the Helmholtz free energy (or Helmholtz energy) is a thermodynamic potential that measures the useful work obtainable from a closed thermodynamic system at a constant temperature . The change in the Helmholtz energy during a process is equal to the maximum amount of work that the system can perform in a thermodynamic process ...
The maximum work is thus regarded as the diminution of the free, or available, energy of the system (Gibbs free energy G at T = constant, P = constant or Helmholtz free energy F at T = constant, V = constant), whilst the heat given out is usually a measure of the diminution of the total energy of the system (internal energy).
The Helmholtz free energy is in ISO/IEC standard called Helmholtz energy [1] or Helmholtz function. It is often denoted by the symbol F, but the use of A is preferred by IUPAC, [5] ISO and IEC. [6] These five common potentials are all potential energies, but there are also entropy potentials.
Historically, the term 'free energy' has been used for either quantity. In physics, free energy most often refers to the Helmholtz free energy, denoted by A (or F), while in chemistry, free energy most often refers to the Gibbs free energy. The values of the two free energies are usually quite similar and the intended free energy function is ...
The Helmholtz free energy is a useful quantity when studying thermodynamic transformations in which the temperature is held constant. Although the reduction in the number of variables is a useful simplification, the main advantage comes from the fact that the Helmholtz free energy is minimized at equilibrium with respect to any unconstrained ...
Calculation of surface energy from first principles (for example, density functional theory) is an alternative approach to measurement. Surface energy is estimated from the following variables: width of the d-band, the number of valence d-electrons , and the coordination number of atoms at the surface and in the bulk of the solid.
The differential form of Helmholtz free energy is = = (), = From symmetry of second derivatives = and therefore that = The other two Maxwell relations can be derived from differential form of enthalpy = + and the differential form of Gibbs free energy = in a similar way.